Cyclohexanone derivatives, process for their production and intermediate products of the process

ABSTRACT

Described are cyclohexanone derivatives of the formula (I), a method of preparing them and intermediates used in their preparation. ##STR1##

This is the U.S. National stage Application of PCT/EP95/02279, filedJun. 13, 1995 now WO 96/00207 published Jan. 4, 1996.

The following invention relates to cyclohexanone derivatives of generalformula I, ##STR2## in which Y and Y' can be the same or different.Specifically, Y and Y' can each mean a hydrogen atom, an alkanoyl groupwith 1 to 9 carbon atoms or an aroyl group or an alkyl-substituted oraryl-substituted or mixed aryl-alkyl-substituted silyl group or anotherstandard hydroxyl protective group (see T. W. Greene and P. G. M. Wuts,Protective Groups in Organic Synthesis (2nd Ed.), pp. 10-118, Wiley,1991).

Y and Y' preferably mean the acetyl, propionyl, pivaloyl or benzoylgroup or the trimethylsilyl (TMS), triethylsilyl (TES),tert-butyldimethylsilyl (TBDMS), tert-butyldiphenylsilyl (TBDPS) ortriisopropylsilyl protective group (TIPS) or the methoxymethyl (MOM),methoxyethoxymethyl (MEM), ethoxyethyl (EE), trimethylsilylethoxymethyl(SEM), tetrahydrofuranyl (THF) or tetrahydropyranyl group (THP).

This invention further relates to a process for the production of thecyclohexanone derivatives of general formula I and intermediate productsfor synthesis of vitamin D-A-ring fragments and 1α-hydroxy vitamin Dderivatives.

Especially preferred are the following cyclohexanone derivatives:

(3S,5S)-3,5-Bisdimethyl(1,1-dimethylethyl)silyl!oxy!-2-methylcyclohexanone

(3S,5S)-3,5-bis(1,1-dimethylethyl)-diphenylsilyl!oxy!-2-methylcyclohexanone

(3S,5S)-3,5-bis (triethylsilyl)oxy!-2-methylcyclohexanone

(3S,5S)-3,5-bis(acetyloxy)-2-methylcyclohexanone

(3S,5S)-3,5-bis(2,2-dimethyl-1-oxopropoxy)-2-methylcyclohexanone

(3S,5S)-3,5-bis(benzoyloxy)-2-methylcyclohexanone

(3S,5S)-3,5-bis(1-ethoxyethoxy)-2-methylcyclohexanone.

In addition, the following intermediate products of synthesis as well asthe process for their production are claimed, ##STR3## in which A and Btogether mean a free or protected carbonyl group (protective groups:dialkoxyketal, 1,3-dioxane, 1,3-dioxolane, dialkylhydrazone,tosylhydrazone, oxime, alkyl- or benzyloxime ether, or A or B means ahydrogen atom and the corresponding other group B or A means a hydroxygroup, which can be free or protected (protective groups: benzyl ether,p-methoxybenzyl ether, o-, m-, p-nitrobenzyl ether, TBDMS ether, TIPSether, TBDPS ether, TES ether, MOM ether, MEM ether, SEM ether, EEether, THP ether, THF ether or the like). The meanings for Y and Y'correspond to the groups that are indicated for general formula I.

Especially preferred are the following intermediate products:

(1S,5S)-1,5-Bis(1-methylethenyl)-2-methyl-3-(phenylmethoxy)cyclohexane

(1S,3S)-1,1'- 4-methyl-5-(phenylmethoxy)-1,3-cyclohexanediyl!bisethanone!

(1S,5R)-1,5-bis(acetyloxy)-2-methyl-3-(phenylmethoxy)-cyclohexane

(1S,3S)-4-methyl-5-(phenylmethoxy)-1,3-cyclohexanediol

(1S,5R)-1,5-bisdimethyl(1,1-dimethylethyl)silyl!oxy!-2-methyl-3-(phenylmethoxy)cyclohexane

(3S,5R)-3,5-bisdimethyl(1,1-dimethylethyl)silyl!oxy!-2-methylcyclohexanol

(3S,5R)-3,5-bis(acetyloxy)-2-methylcyclohexanol

(E)-(3S,5S)-3,5-bis(1-methylethenyl)-2-methylcyclohexanone oxime

(Z)-(3S,5S)-3,5-bis(1-methylethenyl)-2-methylcyclohexanone oxime

(E)-(3S,5S)-3,5-bis(1-methylethenyl)-2-methylcyclohexanone-O-methyloxime

(Z)-(3S,5S)-3,5-bis(1-methylethenyl)-2-methylcyclohexanone-O-methyloxime

(E)-(1S,3S)-1,1'- 5-(hydroxyimino)-4-methyl-1,3-cyclohexanediyl!bisethanone!

(Z)-(1S,3S)-1,1'- 5-(hydroxyimino)-4-methyl-1,3-cyclohexanediyl!bisethanone!

(E)-(1S,3S)-1,1'- 5-(methoxyimino)-4-methyl-1,3-cyclohexanediyl!bisethanone!

(Z)-(1S,3S)-1,1'- 5-(methoxyimino)-4-methyl-1,3-cyclohexanediyl!bisethanone!

(E)-(3S,5R)-3,5-bis(acetyloxy)-2-methylcyclohexanone oxime

(E)-(3S,5R)-3,5-bis(acetyloxy)-2-methylcyclohexanone-O-methyloxime

(Z)-(3S,5R)-3,5-bis(acetyloxy)-2-methylcyclohexanone-O-methyloxime

(E)-(3S,5R)-3,5-dihydroxy-2-methylcyclohexanone oxime

(Z)-(3S,5R)-3,5-dihydroxy-2-methylcyclohexanone oxime

(E)-(3S,5R)-3,5-dihydroxy-2-methylcyclohexanone-O-methyloxime

(Z)-(3S,5R)-3,5-dihydroxy-2-methylcyclohexanone-O-methyloxime

(E)-(3S,5R)-3,5-bisdimethyl(1,1-dimethylethyl)silyl!oxy!-2-methylcyclohexanone oxime

(Z)-(3S,5R)-3,5-bis(dimethyl(1,1-dimethylethyl)silyl!oxy!-2-methylcyclohexanone oxime

(E)-(3S,5R)-3,5-bisdimethyl(1,1-dimethylethyl)silyl!oxy!-2-methylcyclohexanone-O-methyloxime

(Z)-(3S,5R)-3,5-bis(dimethyl(1,1-dimethylethyl)silyl!oxy!-2-methylcyclohexanone-O-methyloxime

(1S,5S)-1,5-bis(1-methylethenyl)-3-(1,1-dimethylethyl)diphenylsilyl!oxy!-2-methylcyclohexane

(1S,3S)-1,1'- 5-(1,1-dimethylethyl)diphenylsilyl!oxy!-4-methyl-1,3-cyclohexanediyl!bisethanone!

(1S,5S)-1,5-bis(acetyloxy)-3-(1,1-dimethylethyl)diphenylsilyl!oxy!-2-methylcyclohexane

(1S,3S)-5-(1,1-dimethylethyl)diphenylsilyl!oxy!-4-methyl-1,3-cyclohexanediol

(1S,5S)-1,5-bis(1-ethoxyethoxy)-3-(1,1-dimethylethyl)diphenylsilyl!oxy!-2-methylcyclohexane

(3S,5R)-3,5-bis(1-ethoxyethoxy)-2-methylcyclohexanol

The advantage of this invention lies in the fact that starting fromcarvone, an A-ring fragment is created, which right in the first stepcontains identical substitution patterns in the 3- and 5-positions, andall subsequent synthetic manipulations at these sites can proceedsimultaneously. Within the prior art, already similar syntheses, alsostarting from carvone, are described, in which the sites are synthesizedin the 3- and 5-positions with the aid of a prolonged, complex synthesismethod to obtain a trans-diol structure Tetrahedron Letters, Vol. 28,2099-2102 (1987) and J. Org. Chem. 54, 3515-3517 (1989)!.

All compounds of general formulas I, IX, X and XII can be produced fromthe corresponding precursors by standard reactions, cf. reactiondiagrams 1 and 2.

Derivatives of general formula I can be converted readily to1α-hydroxy-vitamin D-A-ring fragments of general formula II, ##STR4## inwhich Y and Y' have the already described meaning. Type II compounds areknown in the literature and can be converted with suitable CD ringfragments and established sequence chemistry, as is generally known, to1α-hydroxy-vitamin D analogs B. Lythgoe et al. Tetrahedron Lett. 3649(1973), J. Chem. Soc. Perk. I 2654 (1974), A. Mourino et al. TetrahedronLett. 29, 1203 (1988), W. H. Okamura et al. J. Org. Chem. 54, 4072(1989) and EP 0 521 550 A2!.

In this case, primarily type III eninene derivatives are produced,##STR5## from which 1α-hydroxy-vitamin D derivatives of general formulaIV can be produced by Lindlar hydrogenation of the triple bond into thecis-double bond and subsequent thermally induced 1,7-hydrogendisplacement. In this case, radical R means one of the natural vitamin Dside chains or one of the artificial vitamin D side chains known in theliterature. ##STR6##

This invention thus represents a new process for the synthesis ofintermediate products for the production of 1α-hydroxy-vitamin Danalogs.

The latter can be used in the selection of suitable side chains for theproduction of pharmaceutical agents for treating specific diseases(psoriasis, malignant tumors, acne, auto-immune diseases, wound healing,osteoporosis, etc.). Examples of corresponding derivatives, theirbiological actions and the target indications are documented in thefollowing patent applications:

Schering AG EP 421 561, WO 91/12238, DE 40 03 854, DE 41 01 953, DE 4141 746, WO 93/12081, DE 42 20 757, WO 94/00428, DE 42 21 961 WO94/00429, DE 42 34 382, DE 43 17 415, WO 94/07853.

The conversion of I into II can be accomplished by reaction withlithium, sodium or potassium acetylide or the correspondingmono-trimethylsilylacetylide to a compound of general formula V ##STR7##whereby Z means a hydrogen atom or the trimethylsilyl group. II isobtained by subsequent water elimination (e.g., POCl, pyridine; SOCl₂,pyridine; heating with anhydrous copper sulfate, Burgess reagent; actionof diethylamino sulfur trifluoride; action of acid, such as mineralacids, acetic acid, oxalic acid, trifluoroacetic acid) or conversion ofthe hydroxyl group to a leaving group with subsequent elimination (e.g.,mesylate or tosylate and base action; xanthogenate or acetate andpyrolysis) followed by possible separation of the regioisomers.

Another strategy comprises the reaction of I to a thermodynamicallycontrolled enol derivative of general formula VI (e.g., enol triflateX=OSO₂ CF₃ ; enol nonaflate X=OSO₂ C₄ F₉ ; vinyl halide X=F, Cl, Br, I)and coupling with a suitable acetylene (e.g., trimethylsilyl acetylene)or the reaction of the corresponding vinyl stannanes (X=alkyl₃ Sn) orvinyl boric acids or their esters (X=B(OH)₂, B(OR)₂) with haloacetylenein palladium-catalyzed reactions to II K. Ritter Synthesis 735 (1993),S. Cacchi Synthesis 320 (1986), L. Brandsma Synth. Comm. 20, 1889(1990), N. Miyaura et al. Tetrahedron Lett. 22, 127 (1981)!. Here, thepossibility also arises of directly coupling said enol derivative VI,whereby X=OSO₂ CF₃ ; X=OSO₂ C₄ F₉ ; X=F, Cl, Br, I; with a suitablysubstituted vitamin D-CD fragment e.g., VII, W. H. Okamura et al., J.Org. Chem. 49, 2152 (1984)!. ##STR8##

The synthesis of the compounds of general formula I according to theinvention is carried out in a new, very direct method that starts from(S)-carvone (commercially available), which is converted in a conjugatedaddition with a suitable organometallic compound (isopropenyl-cuprate,isopropenyl magnesium halides under copper catalysis) to compound VIII.##STR9##

The introduction of the isopropenyl group is carried out quiteselectively from the β-side of the molecule, whereby the absolute andrelative configuration that is required for the calcitriol derivative isbuilt up in the subsequent 1- and 3-positions. An advantage of thisapproach, moreover, is the similar substitution of these sites, so thatall chemical manipulations can be performed simultaneously.

The keto group in VIII is now protected under standard conditions asketal, hydrazone or the like or is reduced to alcohol with a reducingagent (e.g., NaBH₄, LiAlH₄, DIBAH, Super-Hydride, Selectride,Meerwein-Ponndorf conditions, boranes), which is then provided with aprotective group, which must tolerate the subsequent reaction conditions(e.g., benzyl ether, even aryl-substituted; TBDPS ether; TBDMS ether,etc.), whereby derivatives of general formula IX are produced, ##STR10##in which A and B have the meanings already described above.

Below, the two vinyl groups are degraded to form the correspondingmethyl ketones of general formula X. ##STR11##

For this reaction, an ozonolysis with mild reductive working-up(triphenylphosphine, dimethylsulfide, amines) is suitable. Thedihydroxylation of the double bonds under standard conditions (e.g.,KMnO₄ ; OSO₄, reoxidizing agent) followed by glycol cleavage (e.g.,NaIO₄ ; HIO₄ ; Pb(OAc)₄) is also possible. In a double Baeyer-Villigerreaction, X is then converted to diacetate XI. ##STR12##

A survey on the considerable number of applicable methods provides areview article: G. R. Krow Org. React. 43, 251 (1993). To be emphasizedis a novel method that does not require the use of highly concentratedoxidizing agents such as 90% hydrogen peroxide or 100% MCPBA: urea/H₂ O₂adduct, trifluoroacetic anhydride M. S. Cooper, H. Heaney, A. J.Newbold, W. R. Sanderson Synlett 533 (1990)!. This method appearsespecially suitable for industrial use and actually provides the bestresults in the case indicated here. Then, the acetates can cleave toform the free hydroxy groups and other protective groups are introduced(e.g., TBDMS, EE), whereby the compound of general formula XII isobtained. The acetates can also be retained, however. ##STR13##

The definitions of A, B and Y as well as Y' were already given earlier.

If A and B mean a carbonyl protective group, the cleavage of this group(e.g., ketal: acid catalysis; oxime alkyl ether: TiCl₃, DIBAH or sodiumbisulfite; oximebenzyl ether: hydrogenolysis) results directly in thecompound of general formula I, while for A=hydrogen and B=hydroxyprotective group or vice versa, the corresponding cleavage (silylgroups; TBAF, HF or HF/pyridine; benzyl ether: hydrogenolysis) yieldsthe compound of general formula XIII. ##STR14##

The reaction to I is then carried out by oxidation with a suitableoxidizing agent, e.g., RuO₂ /NaIO₄ K. Sakai Tetrahedron Asymmetry 3, 297(1992)! or Swern conditions. As an alternative, other oxidation methodsare also conceivable: e.g., PCC, PDC, Dess-Martin reagent, BaMnO₄.

By the described new process and taking commercially available(S)-carvone as a starting material, a type II 1α-hydroxy-vitaminD-A-ring fragment is produced, whereby all chemical manipulations can beimplemented very easily and can be readily scaled up to productionlevels.

The total yield of the sequence, without expensive optimizing tests,lies between 16 and 18% over 11 stages. This process thus offersconsiderable advantages compared to the syntheses of II or correspondingprecursor derivatives that are described in the literature A. Mourino etal. Tetrahedron Lett. 28, 2099 (1987), M. R. Uskokovic et al.Tetrahedron Lett. 28, 2095 (1987), S. Takano et al. J. Org. Chem. 54,3515 (1989)!. These processes are of academic interest at best due inpart to poor yields as well as the use of more expensive reactionconditions or expensive, harmful reagents.

The following examples are used to explain the invention.

EXAMPLES (3S,5S)-3,5-Bis(1-methylethenyl)-2-methylcyclohexanone 1

95 ml of a 1.7M tert-butyllithium solution in pentane (160 mmol) isslowly added in drops to a solution of 9.68 g (80 mmol) of2-bromo-1-propene in 160 ml of absolute diethyl ether at -78° C., and itis stirred for 1 more hour at the given temperature. Then, 3.58 g (40mmol) of copper(I) cyanide is added, and the reaction mixture is slowlyheated to -20° C. and kept for 30 minutes at this temperature.Ultimately, the reaction mixture is again cooled to -78° C. and mixedwith 4.51 g (30 mmol) of (S)-carvone.

Then, the reaction mixture is slowly heated to room temperature andcarefully quenched with saturated ammonium chloride solution. Afterdilution with ethyl acetate, it is washed another three times withsaturated ammonium chloride solution, and the combined aqueous phasesare re-extracted another two times with ethyl acetate. The combinedorganic phases are washed with saturated sodium chloride solution, driedon sodium sulfate, filtered, and the solvent is drawn off in a rotaryevaporator. The residue is purified on a silica gel column (mobilesolvent: EE:H=1:9, R_(f) =0.8).

5.48 g (28.47 mmol) of title compound 1 is obtained as a colorlessliquid.

In general, the spectroscopic data of the main diastereomer areindicated.

¹ H-NMR (300 MHz, CDCl₃): δ=s 4.95 ppm (1H); s 4.80 ppm (1H); s 4.75 ppm(1H); s 4.525 ppm (1H); m 2.75-2.55 ppm (3H); dd 2.525 ppm 5+1!Hz (1H);ddd 2.30 ppm 15+10+1!Hz (1H); m 2.00 ppm (1H); dd 1.825 10+5!(1H); s1.725 ppm (3H); s 1.70 ppm (3H); d 1.075 ppm 7.5!(3H)

MS (EI): m/z=192 (M⁺) 3%!; 177 (M⁺) 2%!; 95 32%!; 83 100%!

IR (CHCl₃): ν=1701, 1451, 1377, 901 cm⁻¹

Production of 1 by Grignard Reaction

5.4 g (220 mmol) of magnesium chips in 60 ml of THF is introduced, and25.41 g (210 mmol) of 2-bromopropene in 200 ml of THF is added in drops,so that the mixture boils easily. It is stirred for 15 more minutes andthen cooled to 0° C. 396 mg (4 mmol) of copper(I) chloride is now added,stirred for another 15 minutes at 0° C. and ultimately 22.53 g (150mmol) of (S)-carvone in 100 ml of THF is added. The reaction mixture isnow heated slowly to room temperature and worked up analogously to theabove cuprate addition, whereby 25.38 g (132 mmol) of title compound 1is obtained as a colorless liquid.

(3S,5S)-3,5-Bis(1-methylethenyl)-2-methylcyclohexanol 2

1.14 g (30 mmol) of sodium borohydride is added in portions to asolution of 5.47 g (28.40 mmol) of 1 in 150 ml of absolute methanol atroom temperature, and the reaction mixture is stirred for 4 more hours.

For working-up, it is hydrolyzed with water, extracted several timeswith dichloromethane and the combined organic phases are washed withsaturated sodium chloride solution, dried on sodium sulfate, and thesolvent is drawn off in a rotary evaporator. The residue is purified ona silica gel column (mobile solvent: EE:H=2:8; R_(f) =0.2).

4.55 g (23.43 mmol) of title compound 2 is obtained as a colorlessliquid.

¹ H-NMR (300 MHz, CDCl₃): δ=q 4.90 ppm 1!Hz (1H); m 4.85 ppm (2H); s4.65 ppm (1H); ddd 4.00 12.5+5+5!Hz (1H); s(br) 2.50 ppm (1H); m 2.2 ppm(2H); dm 1.95 ppm 12.5!Hz (1H); s 1.725 ppm (3H); s 1.70 ppm (3H); m1.65 ppm (4H); d 0.75 ppm 7.5)Hz (3H)

MS (EI): m/z=194 (M⁺) 5%!; 177 (M⁺ --OH) 47%!; 176 (M⁺ --H₂ O) 48%!; 13380%!; 107 81%!; 93 45%!

Production of 2 by DIBAH reduction of 1

19.2 g (100 mmol) of 1 in 400 ml of toluene is introduced, and 100 ml(120 mmol) of DIBAH in toluene is added in drops at -78° C. It is heatedslowly to room temperature, isopropanol/water is added and stirred for30 more minutes. The precipitate is filtered off, and the filtrate iswashed with sodium chloride solution, dried on sodium sulfate andconcentrated by evaporation. The residue is chromatographed on silicagel (mobile solvent: EE:H=2:8), whereby 17.49 g (90.03 mmol) of titlecompound 2 accumulates as a colorless liquid.

(1S,5S)-1,5-Bis(1-methylethenyl)-2-methyl-3-(phenylmethoxy)cyclohexane 3

1.8 g (60 mmol) of an 80% sodium hydride suspension is added in portionsto a solution of 4.50 g (23.16 mmol) of 2 in 60 ml of THF at roomtemperature, and it is stirred for 1 more hour. Then, 10.26 g (60 mmol)of benzyl bromide is added in drops at the given temperature. Inaddition, a spatula tip full of dimethylaminopyridine is added, and thereaction mixture is stirred overnight at room temperature.

For working-up, it is hydrolyzed with water and extracted with hexane.The combined organic phases are washed with saturated sodium chloridesolution, dried on sodium sulfate, filtered, and the solvent is drawnoff in a rotary evaporator. The residue is purified on a silica gelcolumn (mobile solvent: hexane; R_(f) =0.9).

5.08 g (17.87 mmol) of title compound 3 is obtained as a colorlessliquid.

¹ H-NMR (300 MHz, CDCl₃): δ=m 7.35 ppm (5H); dd 4.875 7.5+2.5!Hz (1H); s4.75 ppm (1H); s 4.65 ppm (1H); dd 4.6 ppm 7.5+2.5!Hz (1H); s 4.55 ppm(2H); ddd 3.7 ppm 7.5+5+5!Hz (1; s(br) 2.55 ppm (1H); m 2.45 ppm (1H); m2.15 ppm (1H); m 2.05 ppm (1H); m 1.75 ppm (9H); d 0.80 ppm 7.5!Hz (3H)

MS (EI): m/z=284 (M⁺) 7%!; 282 25%!; 193 (M⁺ --Bn) 7%!; 91 (Bn) 100%!

(1S,3S)-1,1'-4-methyl-5-(phenylmethoxy)-1,3-cyclohexanediyl!bisethanone!4

A weak ozone gas stream passes through a solution of 5.37 g (18.87 mmol)of 3 in 100 ml of absolute dichloromethane at -78° C. for about 30minutes. After the reaction is completed (TLC monitoring), 10.5 g (40mmol) of triphenylphosphine is added, and the reaction mixture is slowlyheated to room temperature.

For working-up, it is diluted with dichloromethane, washed with water,the combined aqueous phases are re-extracted with dichloromethane andthe combined organic phases are washed with saturated sodium chloridesolution, dried on sodium sulfate, filtered off, and the solvent isdrawn off in a rotary evaporator. The residue is purified on a silicagel column (mobile solvent: EE:H=8:2; R_(f) =0.1). 2.29 g (7.94 mmol) oftitle compound 4 is obtained as a colorless liquid.

¹ H-NMR (300 MHz, CDCl₃): δ=m 7.3 ppm (5H); d 4.6 ppm 12!Hz (1H); d 4.5ppm 12!Hz (1H); ddd 3.65 ppm 7.5+5+5!Hz (1H); m 2.85 ppm (1H); m 2.65ppm (2H); s 2.12 ppm (3H); s 2.10 pm (3H); m 1.9-1.6 ppm (4H); d 0.85ppm 7.5!Hz (3H)

MS (EI): m/z=288 (M⁺) 1%!; 245 (M⁺ --CH₃ CHO) 5%!; 197 (M⁺ --Bn) 4%!; 91(Bn) 100%)!

IR(CHCl₃): ν=3034, 1706, 1357, 1262, 1095 cm⁻¹

(1S,5R)-1,5-Bis(acetyloxy)-2-methyl-3-(phenylmethoxy)cyclohexane 5

20.95 g (154 mmol) of potassium dihydrogen phosphate and 15.05 g (160mmol) of urea/H₂ O₂ adduct (Merck) are added to a solution of 2.28 g(7.9 mmol) of 4 in 160 ml of absolute dichloromethane at roomtemperature. Then, 8.40 g (40 mmol) of trifluoroacetic anhydride isslowly added in drops. It is stirred for 2 more hours at 40° C.

For working-up, it is quenched with saturated sodium bicarbonate,diluted with dichloromethane, the organic phase is washed once each withsaturated sodium sulfite solution, water and saturated sodium chloridesolution, dried on sodium sulfate, filtered off, and the solvent isdrawn off in a rotary evaporator. Two products, which are separated on asilica gel column (mobile solvent: EE:H=4:6; F₁ =1.32 g (4.11 mmol)R_(f1) =0.6 (diacetate); F₂ =0.53 g (1.74 mmol) R_(f2) =0.5(monoacetate), are obtained. The monoacetate was again subjected to theabove procedure.

Spectroscopic data for 5:

¹ H-NMR (300 MHz, CDCl₃): δ=m 7.35 ppm (5H); m 5.2 ppm (1H); m 5.1 ppm(1H); d 4.55 ppm 12!Hz (1H); d 4.5 ppm 12!Hz (1H); ddd 3.8 ppm7.5+5+5!Hz (1H); m 2.6 ppm (1H); s 2.1 ppm (3H).; s 2.05 ppm (3H); m1.85 ppm (4H); d 0.95 ppm 7.5!Hz (3H)

MS (EI): m/z=200 3%!; 169 5%!; 109 25%!; 91 (Bn) 100%!

IR(CHCl₃): ν=1730, 1372, 1252, 1028 cm⁻¹

(1S,3S)-4-Methyl-5-(phenylmethoxy)-1,3-cyclohexanediol 6

378 mg (7 mmol) of sodium methanolate is added to a solution of 1.15 g(3.16 mmol) of 5 in 10 ml of absolute methanol at room temperature, andit is stirred for 24 hours at the given temperature.

For working-up, it is neutralized with saturated ammonium chloridesolution and extracted with dichloromethane. The combined organic phasesare washed with saturated sodium chloride solution, dried on sodiumsulfate, filtered off, and the solvent is drawn off in a rotaryevaporator. The residue is purified on a silica gel column (mobilesolvent: EE; R_(f) =0.3).

558 mg (2.36 mmol) of title compound 6 is obtained as a crystallinesubstance.

¹ H-NMR (300 MHz, CDCl₃): δ=m 7.35 ppm (5H); d 4.7 ppm 12!Hz (1H); d 4.4ppm 12!Hz (1H); m 4.25 ppm (1H); m 3.9 ppm (1H); s(br) 3.8 ppm (1H); m2.5 ppm (1H); m 2.3 ppm (2H); m 1.8-1.3 ppm (4H); d 1.2 ppm 7.5!Hz (3H)

MS (EI): m/z=218 (M⁺ --H₂ O) 2%!; 107 12%!; 91 (Bn) 100%!

(1S,5R)-1,5-Bisdimethyl(1,1-dimethylethyl)silyl!oxy!-2-methyl-3-(phenylmethoxy)-cyclohexane7

557 mg (2.36 mmol) of 6 in 5 ml of absolute DMF is instilled in asolution of 1.51 g (10 mmol) of TBDMSCl and 1.36 g (20 mmol) ofimidazole in 10 ml of absolute DMF at room temperature, and it isstirred overnight at the given temperature.

For working-up, it is diluted with hexane, hydrolyzed with water andshaken out with saturated ammonium chloride solution. The combinedaqueous phases are re-extracted several times with hexane. The combinedorganic phases are washed with saturated sodium chloride solution, driedon sodium sulfate, filtered and the solvent is drawn off in a rotaryevaporator. The residue is purified on a silica gel column (mobilesolvent: hexane; R_(f) =0.9).

832 mg (1.79 mmol) of title compound 7 is obtained as a colorlessliquid.

¹ H-NMR (300 MHz, CDCl₃): δ=m 7.4 ppm (5H); d 4.6 ppm 12!Hz (1H); d 4.45ppm 12!Hz (1H); m 4.1 ppm (2H); ddd 3.8 ppm 10+5+5!Hz; m 2.4 ppm (1H); m1.7 ppm (1H); m 1.55 ppm (1H); d 0.95 ppm 7.5!Hz (3H); s 0.9 ppm (9H); s0.85 ppm (9H); 4×s 0.75-0.5 ppm (12H)

MS (EI): m/z=449 (M⁺ --Me) 1%!; 407 57%!; 318 38%!; 199 28%!; 157 19%!;91 100%!

(3S,5R)-3,5-Bisdimethyl(1,1-dimethylethyl)silyl!oxy!-2-methylcyclohexanol 8

A spatula tip full of 10% Pd/C is added to a solution of 1.14 g (2.45mmol) of 7 in 60 ml of absolute ethanol. The reaction flask is equippedwith a hydrogen balloon, and it is stirred overnight.

For working-up, it is filtered off, and the filter cake is flushedthoroughly with ethanol. Finally, the solvent is concentrated byevaporation in a rotary evaporator, and the residue is purified on asilica gel column (mobile solvent: EE:H=3:7; R_(f) =0.6). 735 mg (1.96mmol) of title compound 8 is obtained as a colorless liquid.

¹ H-NMR (300 MHz, CDCl₃): δ=tt 4.3 ppm 12+4!Hz (1H); m 4.02 ppm (1H);d(br) 3.82 ppm 9!Hz (1H); m 2.32 (1H); m 2.05 ppm (1H); m 1.48 ppm (1H);d 1.10 ppm 7.5!Hz (3H); s 0.9 ppm (9H); s 0.88 ppm (9H); 4×s 0.75-0.5ppm (12H)

MS (EI): m/z=317 (M⁺ --Bu) 7%!; 241 (M⁺ --tBDMSiOH) 8%!; 227 30%!; 19975%!; 185 81%!; 159 50%!; 157 47%!; 115 30%!; 75 99%!; 73 100%!

(3S,5S)-3,5-Bisdimethyl(1,1-dimethylethyl)silyl!oxy!-2-methylcyclohexanone 9

547 mg (7 mmol) of DMSO is slowly added in drops to a solution of 444 mg(3.5 mmol) oxalyl chloride in 20 ml of absolute dichloromethane at -78°C. It is stirred for 20 more minutes at the given temperature. Then, 592mg (1.58 mmol) of 8 in 5 ml of absolute dichloromethane is added, and itis stirred again for 15 more minutes. Then, 2.83 g of triethylamine isadded, and the reaction mixture is slowly heated to room temperature.

For working-up, dichloromethane is added and acidified with dilute HCl.The aqueous phase is re-extracted another two times withdichloromethane, the combined organic phases are washed with saturatedsodium chloride solution, dried on sodium sulfate, filtered off, and thesolvent is drawn off in a rotary evaporator. The residue ischromatographed on a silica gel column (mobile solvent: EE:H=2:8; R_(f)=0.4).

550 mg (1.48 mmol) of title compound 9 is obtained as a white,crystalline substance.

¹ H-NMR (300 MHz, CDCl₃): δ=m 4.3 ppm (1H); m 4.15 ppm (1H); ddd 2.7 ppm15+5+2!Hz (1H); m 2.4 ppm (2H); m 2.2 ppm (1H); m 1.8 ppm (1H); d 1.05ppm 7.5!Hz (3H); s 0.9 ppm (9H); s 0.85 ppm (9H); s 0.5 ppm (12H)

MS (EI): m/z=315 (M⁺ --Bu) 27%!; 199 5%!; 157 100%!; 133 8%!; 115 13%!;75 16%!; 73 22%!

IR(CHCl₃): ν=2957, 2931, 2886, 2858, 1713, 1472, 1257, 1097, 1004, 838cm⁻¹

(3S,5s)-3,5-Bisdimethyl(1,1-dimethylethyl)silyl!oxy!-1-ethinyl-2-methylcyclohexanol 10

At 0° C., acetylene is introduced into 50 ml of THF for 20 minutes. 1.25ml n-Butyllithium solution (1.6M in hexane, 2 mmol) is added in dropsand stirred for 20 more minutes at this temperature. Then, 215 mg (0.58mmol) of 9 in 2 ml of THF is added in drops and stirred for 2 hours.Then, it is quenched with saturated ammonium chloride solution, dilutedwith ethyl acetate, and the organic phase is washed with saturatedsodium chloride solution, dried on sodium sulfate and the solvent isremoved. The residue is purified on silica gel by column chromatography(mobile solvent: EE:H=4:6, R_(f) =0.6), whereby 163 mg (0.41 mmol) oftitle compound 10 is obtained as a white crystalline substance.

¹ H-NMR (300 MHz, CDCl₃): δ=m 4.22 ppm (1H); m 4.06 ppm (1H); ddd 2.48ppm 15+4+2!Hz (1H); dbr 2.09 ppm (1H); m 1.69 ppm (2H); m 1.58 ppm (1H);d 1.25 ppm 7.5!Hz (3H); s 0.92 ppm (9H); s 0.89 ppm (9H); s 0.1 ppm(12H)

(3S,5R)-3,5-Bisdimethyl(1,1-dimethylethyl)silyl!oxy!-1-ethinyl-2-methyl-1-cyclohexene11

90 mg (0.23 mmol) of 10 in 8 ml of pyridine is introduced, and 50 μl ofthionyl chloride is added under argon. It is stirred for 10 minutes atroom temperature, poured onto ice water and extracted with ethylacetate. The organic phase is washed with sodium bicarbonate solutionand sodium chloride solution, dried on sodium sulfate, the solvent isremoved and the crude product is purified by chromatography on silicagel (mobile solvent: EE:H=1:19; R_(f) =0.9), whereby 71 mg (0.20 mmol)of title compound 11 is obtained as a colorless oil.

¹ H-NMR (300 MHz, CDCl₃): δ=m 4.21 ppm (1H); m 4.09 ppm (1H); s 3.06(1H); sbr 1.93 ppm (3H); s 0.91 ppm (9H); s 0.89 ppm (9H); s 0.6 ppm(12H)

IR (KBr): ν=3310, 2085, 1260, 835 cm⁻¹

MS (EI): m/z=380 (M⁺) 3%!; 365 (M⁺ --Me) 25%!; 323 80%!; 248 100%!

(3S,5R)-3,5-Bis(acetyloxy)-2-methylcyclohexanol 12

A spatula tip full of 10% Pd/C is added to a solution of 60 mg (0.19mmol) of 5 in 10 ml of absolute ethanol. The reaction flask is equippedwith a hydrogen balloon, and it is stirred overnight.

For working-up, it is filtered off, and the filter cake is flushedthoroughly with ethanol. Ultimately, the solvent is concentrated byevaporation in a rotary evaporator, and the residue is purified on asilica gel column (mobile solvent: EE:H=1:1; R_(f) =0.3). 44 mg (0.19mmol) of title compound 12 is obtained as a colorless oil.

¹ H-NMR (300 MHz, CDCl₃): δ=m 5.2 ppm (2H); s (br) 4.0 ppm (1H); s 2.1ppm (3H); m 2.05 ppm (3H); s 2.025 ppm (3H); m 1.65 ppm (3H); d 1.00 ppm7.5!Hz (3H)

(3S,5S)-3,5-Bis(acetyloxy)-2-methylcyclohexanone 13

25 mg of ruthenium dioxide is added to a solution of 50 mg (0.22 mmol)of 12 in 1 ml of tetrachloromethane at room temperature. The suspensionis mixed with 0.85 ml of a 0.28 molar sodium metaperiodate solution(0.24 mmol) in water. After 2 hours of stirring at the giventemperature, another 0.5 ml of the aqueous sodium metaperiodate solution(0.14 mmol) is added, and it is again stirred for 2 hours.

For working-up, the catalyst is filtered off, the suspension is dilutedwith ethyl acetate, and the filter cake is thoroughly rewashed withethyl acetate. The combined organic phases are washed with saturatedsodium chloride solution, dried on sodium sulfate, filtered, and thesolvent is drawn off in a rotary evaporator.

73.4 mg of title compound 13 is obtained as a colorless oil.

¹ H-NMR (300 MHz, CDCl₃): δ=m 5.4 ppm (1H); m 5.2 ppm (1H); ddd 2.9 ppm15+5+2.5!Hz (1H); m 2.6 ppm (1H); m 2.45 ppm (2H); m 2.05 ppm (1H); s2.05 ppm (6H); d 1.05 ppm 7.5!Hz (3H)

(1S,5S)-1,5-Bis(1-methylethenyl)-3-(1,1-dimethylethyl)diphenylsilyl!oxy!-2-methylcyclohexane 14

7.67 g (39.6 mmol) of 2 in 50 ml of DMF is introduced, and 6.54 g (96mmol) of imidazole and 12.5 ml (48 mmol) of tert-butyldiphenylsilylchloride in 80 ml of DMF are added. It is stirred overnight at roomtemperature, and then quenched with sodium chloride solution, extractedwith ethyl acetate, the organic phase is washed with sodium chloridesolution and dried on sodium sulfate. After the concentration byevaporation, the residue is chromatographed on silica gel (mobilesolvent: EE:H=2:8), whereby 17.05 g (39.4 mmol) of title compound 14accumulates as a colorless liquid.

¹ H-NMR (300 MHz, CDCl₃): δ=m 7.70 ppm (4H); m 7.39 ppm (6H); s 4.78 ppm(1H); s 4.60 ppm (1H); s 4.52 ppm (1H); s 4.13 ppm (1H); m 3.95 ppm(1H); m 2.33 ppm (1H); m 2.08 ppm (1H); m 1.2 ppm (1H); m 1.75 ppm (2H);m 1.59 ppm (2H); s 1.59 ppm (3H); s 1.42 ppm (3H); s 1.09 ppm (9H); d0.81 ppm 7!Hz (3H)

(1S,3S)-1,1'- 5-1,1-Dimethylethyl)diphenylsilyl!oxy!-4-methyl-1,3-cyclohexanediyl!bisethanone!15

25.75 g (59.5 mmol) of 14 in 420 ml of dichloromethane and 140 ml ofmethanol are dissolved, and ozone/oxygen mixture (ozone generator) isintroduced at -78° C. until the solution is colored light blue. Excessozone is expelled with nitrogen and then mixed with 9.32 g (150 mmol) ofdimethyl sulfide. It is heated to room temperature, the mixture isconcentrated by evaporation and the residue is chromatographed on silicagel (mobile solvent EE:H=6:4), whereby 41.1 g (55.19 mmol) of titlecompound 15 is obtained as a colorless liquid.

¹ H-NMR (300 MHz, CDCl₃): δ=m 7.69 ppm (4H); m 7.40 ppm (6H); m 3.82 ppm(1H); m 2.64 ppm (1H); dt 2.58 ppm 12+4!Hz (1H); m 2.27 ppm (1H); s 1.98ppm (3H); m 1.78 ppm (3H); s 1.70 ppm (3H); 1.61 ppm (1H); s 1.09 ppm(9H), d 0.83 ppm 7!Hz (3H)

(1S,5S)-1,5-Bis(acetyloxy)-3-(1,1-dimethylethyl)-diphenylsilyl!oxy!-2-methylcyclohexane 16

Analogously to Example 5, 17.68 g (40.5 mmol) of 15 is reacted, whereby16.99 g (36.25 mmol) of title compound 16 accumulates as a colorlessoil.

¹ H-NMR (300 MHz, CDCl₃): δ=m 7.68 ppm (4H); m 7.38 ppm (6H); m 5.05 ppm(1H); m 4.99 ppm (1H); m 3.98 ppm (1H); m 2.37 ppm (1H); s 2.08 ppm(3H); s 1.80 ppm (3H); m 1.70 ppm (3H); 1.58 ppm (1H); s 1.09 ppm (9H);d 1.02 ppm 7!Hz (3H)

(1S,3S)-5-(1,1-Dimethylethyl)diphenylsilyl!oxy!-4-methyl-1,3-cyclohexanediol 17

469 mg (1 mmol) of 16 is dissolved in 10 ml of THF and mixed at 0° C.with 3.4 ml of methylmagnesium bromide solution (3M in THF). After 3hours at this temperature, it is hydrolyzed with ammonium chloridesolution, extracted with ethyl acetate and dried on sodium sulfate. Thesolvent is removed, and the residue is purified on silica gel (mobilesolvent: EE:H=8.2), whereby 231 mg (0.6 mmol) of title compound 17 isobtained.

¹ H-NMR (300 MHz, CDCl₃): δ=m 7.69 ppm (4H); m 7.42 ppm (6H); m 4.41 ppm(1H); m 4.09 ppm (1H); m 3.89 ppm (1H); m 2.32 ppm (1H); m 2.00 ppm(1H); m 1.58 ppm (1H); m 1.42 ppm (1H); 1.28 ppm (1H); s 1.09 ppm (9H);d 1.09 ppm 7!Hz (3H)

(1S,5S)-1,5-Bis(1-ethoxyethoxy)-3- (1,1-dimethylethyl)diphenylsilyl!oxy!-2-methylcyclohexane 18

5.11 g (13.3 mmol) of 17 is stirred with 2.96 g of (41 mmol) of ethylvinyl ether and 327 mg (1.3 mmol) of pyridinium-p-toluene sulfonate in80 ml of dichloromethane at room temperature for 3 hours. Then, it iswashed with sodium chloride solution, dried on sodium sulfate andconcentrated by evaporation. The residue is chromatographed on silicagel (mobile solvent: EE:H=1:1), whereby 6.48 g (12.14 mmol) of titlecompound 18 accumulates.

(3S,5R)-3,5-Bis(1-ethoxyethoxy)-2-methylcyclohexanol 19

6.48 g (12.14 mmol) of 18 and 6.31 g (20 mmol) of tetrabutylammoniumfluoride (hydrate) in 150 ml of THF is stirred overnight at roomtemperature. Then, it is hydrolyzed with sodium chloride solution,extracted with ethyl acetate, washed with sodium chloride solution anddried on sodium sulfate. After concentration by evaporation, the residueis chromatographed on silica gel (mobile solvent: EE:H=8:2), whereby2.41 g (8.3 mmol) of title compound 19 is obtained.

¹ H-NMR (300 MHz, CDCl₃): δ=m 4.78 ppm (2H); m 4.12 ppm (2H); m 3.89 ppm(1H); m 3.68 ppm (2H); m 3.49 ppm (2H); m 2.30 ppm (1H); m 1.70 ppm(1H); m 1.43 ppm (3H); d 1.34 ppm 7!Hz (6H); t 1.21 ppm 7!Hz (6H); d1.09 ppm 7!Hz (3H)

(3S,5S)-3,5-Bis(1-ethoxyethoxy)-2-methylcyclohexanone 20

Analogously to Example 9, 2.4 g (8.3 mmol) of 19 is reacted, whereby2.17 g (7.5 mmol) of title compound 20 accumulates as a colorless oil.

¹ H-NMR (300 MHz, CDCl₃): δ=m 4.74 ppm (2H); m 4.18 ppm (2H); m 3.60 ppm(2H); m 3.48 ppm (2H); m 2.81 ppm (1H); m 2.42 ppm (3H); m 1.83 ppm(1H); d 1.38 ppm 7!Hz (6H); t 1.20 ppm 7!Hz (6H); d 1.09 ppm 7!Hz (3H)

(3S,5)-3,5-Bis(1-ethoxyethoxy)-1-ethinyl-2-methylcyclohexanol 21

2.00 g (6.94 mmol) of 20 ia reacted analogously to Example 10, and 1.87g (5.96 mmol) of title compound 21 is obtained as a colorless oil.

(3S,5S)-3,5-Bis(1-ethoxyethoxy)-1-ethinyl-2-methyl-1-cyclohexene 22

Analogously to Example 11, 1.87 g (5.96 mmol) of 21 is reacted, and 1.39g (4.67 mmol) of title compound 22 is obtained as a yellowish oil.

¹ H-NMR (300 MHz, CDCl₃): m 4.80 ppm (2H); m 4.00 ppm (2H); m 3.63 ppm(2H); m 3.49 ppm (2H); d 3.09 ppm 4!Hz (1H); m 2.54 ppm (1H); m 2.14 ppm(3H); s 2.00 ppm (3H); s 1.95 ppm (3H); d 1.38 ppm 7!Hz (6H); t 1.20 ppm7!Hz (6H) ##STR15##

We claim:
 1. A cyclohexanone compound of formula I,in which Y and Y'each mean a hydrogen atom, an alkanoyl group with 1 to 9 carbon atoms,an aroyl group, an alkyl-substituted or aryl-substituted or mixedaryl-alkyl-substituted silyl or silylalkoxyalkyl group, an alkoxyalkylgroup, a tetrahydrofuranyl group or a tetrahydropyranyl group.
 2. Acyclohexanone compound according to claim 1, in which Y and Y' meanacetyl, propionyl, pivaloyl or benzoyl or trimethylsilyl (TMS),triethylsilyl (TES), tert-butyldimethylsilyl (TBDMS),tert-butyldiphenylsilyl (TBDPS) or triisopropylsilyl (TIPS) ormethoxymethyl (MOM), methoxyethoxymethyl (MEM), ethoxyethyl (EE),trimethylsilylethoxymethyl (SEM), tetrahydrofuranyl (THF) ortetrahydropyranyl (THP) and can be the same or different.
 3. Acyclohexanone compound according to claim 1, namely(3S,5S)-3,5-Bisdimethyl(1,1-dimethylethyl)silyl!oxy!-2-methylcyclohexanone,(3S,5S)-3,5-bis(1,1-dimethylethyl)diphenylsilyl!oxy!-2-methylcyclohexanone,(3S,5S)-3,5-bis (triethylsilyl)oxy!-2-methylcyclohexanone,(3S,5S)-3,5-bis(acetoxy)-2-methylcyclohexanone,(3S,5S)-3,5-bis(2,2-dimethyl-1-oxopropoxy)-2-methylcyclohexanone,(3S,5S)-3,5-bis(benzoyloxy)-2-methylcyclohexanone,(3S,5S)-3,5-bis(1-ethoxyethoxy)-2-methylcyclohexanone.
 4. A process forthe production of a cyclohexanone compound of formula I according toclaim 1, by reaction of (S)-carvone with a copper-containingorganometallic compound to compound VIII, ##STR16## reaction of compoundVIII to the compound of general formula IX ##STR17## subsequentoxidative cleavage of the vinyl group to the corresponding methylketones of general formula X, ##STR18## conversion of the compounds ofgeneral formula X by Baeyer-Villiger oxidation to the diacetate ofgeneral formula XI ##STR19## saponification of the acetate groups andconversion to compounds of general formula XII, ##STR20## in which Y andY' have the meanings mentioned in claims 1 and 2, and in generalformulas IX, X, XI and XII, A and B together mean a free or protectedcarbonyl group, whereby the protective groups are selected fromdialkoxyketal, 1,3-dioxane, 1,3-dioxolane, dialkylhydrazone,tosylhydrazone, oxime, alkyl- or benzyloxime ether or A or B means ahydrogen atom and the corresponding other group B or A means a hydroxygroup, which can be free or protected, whereby the protective groups areselected from benzyl ether, p-methoxybenzyl ether, o-, m-, p-nitrobenzylether, TBDMS ether, TIPS ether, TBDPS ether, TES ether, MOM ether, MEMether, SEM ether, EE ether, THP ether and THF ether, and subsequentcleavage of the ketal or hydrazone group or selective cleavage ofalcohol protective group A or B and oxidation.
 5. A compounds of theformula IX ##STR21## in which A and B together mean a protected carbonylgroup, whereby the protective groups are selected from dialkoxyketal,1,3-dioxane, 1,3-dioxolane, dialkylhydrazone, tosylhydrazone, oxime,alkyl- or benzyloxime ether or A or B means a hydrogen atom and thecorresponding other group B or A means a hydroxy group, which can befree or protected, whereby the protective groups are selected frombenzyl ether, p-methoxybenzyl ether, o-, m-, p-nitrobenzyl ether, TBDMSether, TIPS ether, TBDPS ether, TES ether, MOM ether, MEM ether, SEMether, EE ether, THP ether and THF ether.
 6. A compound of claim 5,whichis:(1S,5S)-1,5-Bis(1-methylethenyl)-2-methyl-3-(phenylmethoxy)cyclohexane,(E)-(3S,5S)-3,5-bis(1-methylethenyl)-2-methylcyclohexanone oxime,(Z)-(3S,5S)-3,5-bis(1-methylethenyl)-2-methylcyclohexanone oxime,(E)-(3S,5S)-3,5-bis(1-methylethenyl)-2-methylcyclohexanone-O-methyloxime,(Z)-(3S,5S)-3,5-bis(1-methylethenyl)-2-methylcyclohexanone-O-methyloximeor (1S,5S)-1,5-bis(1-methylethenyl)-3-(1,1-dimethylethyl)diphenylsilyl!oxy!-2-methylcyclohexane.
 7. A compoundof the formula X ##STR22## in which A and B together mean a free orprotected carbonyl group, whereby the protective groups are selectedfrom dialkoxyketal, 1,3-dioxane, 1,3-dioxolane, dialkylhydrazone,tosylhydrazone, oxime, alkyl- or benzyloxime ether or A or B means ahydrogen atom and the corresponding other group B or A means a hydroxygroup, which can be free or protected, whereby the protective groups areselected from benzyl ether, p-methoxybenzyl ether, o-, m-, p-nitrobenzylether, TBDMS ether, TIPS ether, TBDPS ether, TES ether, MOM ether, MEMether, SEM ether, EE ether, THP ether and THF ether.
 8. A compound ofclaim 7, which is:(1S,3S)-1,1'-4-Methyl-5-(phenylmethoxy)-1,3-cyclohexanediyl!bis ethanone!,(E)-(1S,3S)-1,1'- 5-(hydroxyimino)-4-methyl-1,3-cyclohexanediyl!bisethanone!, (Z)-(1S,3S)-1,1'-5-(hydroxyimino)-4-methyl-1,3-cyclohexanediyl!bis ethanone!,(E)-(1S,3S)-1,1'- 5-(methoxyimino)-4-methyl-1,3-cyclohexanediyl!bisethanone!, (Z)-(1S,3S)-1,1'-5-(methoxyimino)-4-methyl-1,3-cyclohexanediyl!bis ethanone! or(1S,3S)-1,1'- 5-(1,1-dimethylethyl)diphenylsilyl!oxy!-4-methyl-1,3-cyclohexanediyl!bisethanone!.
 9. A compound of the formula XI, ##STR23## in which A and Btogether mean a free or protected carbonyl group, whereby the protectivegroups are selected from dialkoxyketal, 1,3-dioxane, 1,3-dioxolane,dialkylhydrazone, tosylhydrazone, oxime, alkyl- or benzyloxime ether orA or B means a hydrogen atom and the corresponding other group B or Ameans a hydroxy group, which can be free or protected, whereby theprotective groups are selected from benzyl ether, p-methoxybenzyl ether,o-, m-, p-nitrobenzyl ether, TBDMS ether, TIPS ether, TBDPS ether, TESether, MOM ether, MEM ether, SEM ether, EE ether, THP ether and THFether.
 10. A compound of claim 9, whichis:(1S,5R)-1,5-Bis(acetyloxy)-2-methyl-3-(phenylmethoxy)-cyclohexane,(3S,5R)-3,5-bis(acetyloxy)-2-methylcyclohexanol,(E)-(3S,5R)-3,5-bis(acetyloxy)-2-methylcyclohexanone oxime,(Z)-(3S,5R)-3,5-bis(acetyloxy)-2-methylcyclohexanone oxime,(E)-(3S,5R)-3,5-bis(acetyloxy)-2-methylcyclohexanone-O-methyloxime,(Z)-(3S,5R)-3,5-bis(acetyloxy)-2-methylcyclohexanone-O-methyloxime or(1S,5S)-1,5-bis(acetyloxy)-3-(1,1-dimethylethyl)diphenylsilyl!oxy!-2-methylcyclohexane.
 11. Acompound of the formula XII, ##STR24## in which Y and Y' each mean ahydrogen atom, an alkanoyl group with 1 to 9 carbon atoms, an aroylgroup, an alkyl-substituted or aryl-substituted or mixedaryl-alkyl-substituted silyl or silylalkoxyalkyl group, alkoxyalkylgroup, a tetrahydrofuranyl group or a tetrahydropyranyl group, and A andB together mean a free or protected carbonyl group, whereby theprotective groups are selected from dialkoxyketal, 1,3-dioxane,1,3-dioxolane, dialkylhydrazone, tosylhydrazone, oxime, alkyl- orbenzyloxime ether or A or B means a hydrogen atom and the correspondingother group B or A means a hydroxy group, which can be free orprotected, whereby the protective groups are selected from benzyl ether,p-methoxybenzyl ether, o-, m-, p-nitrobenzyl ether, TBDMS ether, TIPSether, TBDPS ether, TES ether, MOM ether, MEM ether, SEM ether, EEether, THP ether and THF ether.
 12. A compound of claim 11, whichis:(1S,3S)-4-Methyl-5-(phenylmethoxy)-1,3-cyclohexanediol,(1S,5R)-1,5-bisdimethyl(1,1-dimethylethyl)silyl!oxy!-2-methyl-3-(phenylmethoxy)cyclohexane,(3S,5R)-3,5-bisdimethyl(1,1-dimethylethyl)silyl!oxy!-2-methylcyclohexanol(3S,5R)-3,5-bis(acetyloxy)-2-methylcyclohexanol,(E)-(3S,5R)-3,5-dihydroxy-2-methylcyclohexanone oxime,(Z)-(3S,5R)-3,5-dihydroxy-2-methylcyclohexanone oxime,(E)-(3S,5R)-3,5-dihydroxy-2-methylcyclohexanone-O-methyloxime,(Z)-(3S,5R)-3,5-dihydroxy-2-methylcyclohexanone-O-methyloxime,(E)-(3S,5R)-3,5-bisdimethyl(1,1-dimethylethyl)silyl!oxy!-2-methylcyclohexanone oxime,(Z)-(3S,5R)-3,5-bisdimethyl(1,1-dimethylethyl)silyl!oxy!-2-methylcyclohexanone oxime,(E)-(3S,5R)-3,5-bisdimethyl(1,1-dimethylethyl)silyl!oxy!-2-methylcyclohexanone-O-methyloxime,(Z)-(3S,5R)-3,5-bisdimethyl(1,1-dimethylethyl)silyl!oxy!-2-methylcyclohexanone-O-methyloxime,(1S,5S)-1,5-bis(acetyloxy)-3-dimethyl(1,1-dimethylethyl)diphenylsilyl!oxy!-2-methylcyclohexane,(1S,3S)-5-(1,1-dimethylethyl)diphenylsilyl!oxy!-4-methyl-1,3-cyclohexanediol,(1S,5S)-1,5-bis(1-ethoxyethoxy)-3-(1,1-dimethylethyl)-diphenylsilyl!oxy!-2-methylcyclohexane or(3S,5R)-3,5-bis(1-ethoxyethoxy)-2-methylcyclohexanol.